Lubricant addition agents



Patented Apr. 12, 1949 UNITED STATES PATENT OFFICE 2,467,176 LUBRICANT ADDITION AGENTS John C. Zimmer, Union, Ejnar W. Carlson. Mountainside, and Gordon W. Duncan, Wcstfleld, N. J., assignors to Standard Oil Development Company, a corporation of Delaware No Drawing.

ApplicationNovember 21, 1944, Serial N0. 564,546

9 Claims. (CL 252-4334) .relatively high temperatures, piston rings have a tendency to become stuck in their grooves. Accumulation of lacquer and/or carbonaceous deposits on the rings and grooves appears to be the most probable reason for this occurrence. The addition of certain types of metal derivatives of organic compounds is known to improve the properties of these oils, such as their oiliness characteristics and their detergent action in engines, particularly manifested in the maintenance of a clean engine condition during operation. Various metal compounds which have been used for such purposes include the metal derivatives of such organic compounds as fatty acids, naphflllienic acids, alcohols, phenols, ketones and the It is also known that calcium and other polyvalent metal salts of petroleum or synthetic sulfonic acids have been used as engine oil detergent addition agents. These materials are effective to a moderate degree but their plastic nature and poor oil-solubility make their use difilcult.

It is an object of the present invention to provide a new class of addition agents for oils which are 'to be used as crankcase lubricants for internal combustion engines and which exhibit to a high degree the desirable properties of, promoting general engine cleanliness, and reducing ring sticking, piston skirt varnish formation and the like. 7

It is a still further object of this invention to prepare lubricating oils for such severe service conditions as are encountered in high speed Diesel engines, which oils possess detergent properties and thereby avoid deposition of lacquer, asphaltenes and varnish-like materials on the pistons, behind the rings and in the ring grooves.

According to the present invention these and other objects are attained by adding small amounts in the order of about 0.1% to 2.5% of an oil-soluble complex polyvalent metal salt of a sulfonic acid. Particularly suitable sulfonate salts for this purpose are those of the alkaline earth metals, e. g. calcium, magnesium, strontium and barium. However, complexes of other polyvalent metal sulfonates .may be used, such as those of aluminum, iron, zinc, cadium, cobalt,

nickel, etc. 1

The petroleum sulfonates which are of major current interest are the soaps of oil-soluble or socalled mahogany" acids, which are usually produced during treatment of lubricating oil distillates with concentrated to fuming sulfuric acid, and remain in the oil after settling out the sludge. These sulfonic acids may be represented as where (R) is one or more alkyl, alkaryl or aralkyl groups and the aromatic nucleus may be a single or condensed ring or a partially hydrogenated ring. The lower molecular weight acids can be extracted from the acid-treated oil by adding a small amount of water, preferablyafter dilution of the oil with kerosene. However, the more desirable high molecular weight (350 to 500) acids, particularly those produced when treating white oil with fuming acid, are normally recovered as sodium soaps by neutralizing the acid oil with sodium hydroxide or carbonatev and extracting with aqueous alcohol. The crude soap extract is first recovered as awater curd after removal of alcohol by distillation and a gravity separation of some of the contaminating salts (sodium carbonate, sulfate and sulfite). The material still contains considerable quantities of salts and consequently is normally purified by readdition of alcohol followed by storage to permit settling of salt brine. The alcohol and water are then stripped out and replaced with a light lubricating oil to yield the commercial purified concentrate, generally containing from 50% to sodium sulfonate.

To prepare polyvalent metal sulfonates, acid treated oils or extracted sulfonic acids may be neutralized directly with an oxide or hydroxide of the desired metal. However it is often more convenient to prepare them from the sodium salts by double decomposition. Thus, the polyvalent metal salts may be made by precip tating the sodium sulfonates from alcoholic solution with a po yvalent metal salt. Or an oil solution of sodium sul-' by precipitating from alcohol solution with calcium chloride, inorganic salts then being removed by washing with water. When these soaps are dehydrated with sufficient oil to give a 25% concentrate a stiff gel-like product, which is only poorly oil-soluble, is obtained. The analysis of a typical sample of such a concentrate is given in the following table:

The data in the above table indicate that these sulfonates are substantially normal calcium sulfonates having a stoichiometric ratio of calcium to sulfonic acid. ,These normal calcium sulfonates, however, exhibit only fair engine detergency and are poorly oil-soluble.

It has now been found that normal polyvalent metal sulfonates tend to form complexes with other metal salts, particularly with inorganic salts, when such salts are present with the sulfonate during the dehydration step. Such complexes, or coordination compounds, are not formed in themanufacture of polyvalent metal sulfonates inasmuch as the inorganic salts are removed by water washing before the sulfonates are dehydrated in the presence of oil as described above. Furthermore, it is necessary that the dehydration be carried substantially to completion in order to form the complex sulfonates.

However, if when converting a sodium sulfonate to a polyvalent metal derivative by the methods outlined above, some of the inorganic salt employed for the conversion is allowed to remain during the final dehydration step, a porbility is readily noted during the manufacture of the coordination compounds. A 25 to 30% concentrate of a normal sulfonate of a polyvalent metal in oil will be very viscous and often gel-like in nature but when the sulfonate is converted to a coordination compound the concentrate will be found to be quite fluid. Thus, it may be said that the process of the present invention serves a to fluidize the sulfonates.

Other coordination compounds may be prepared by adding other'metal salts or oxides or hydroxides to the polyvalent metal sulfonate in addition to or in place of the inorganic salt remaining from the conversion of the sodium sulfonate to a polyvalent metal salt. For example,

if sodium sulfonate to a polyvalent metal salt. For example, if sodium sulfonate has been converted to calcium sulfonate, excess calcium chloride may be allowed to remain, and then before dehydration calcium hydroxide may also be added. Or, if a different type of coordination compound is to be formed, the excess calcium chloride from the conversion step may be removed by water washing or by other suitable means, and other materials such as aluminum acetate or lithium chloride may be added before the dehydration step. sulfonates prepared by direct neutralization of sulfonic acids may be similarly converted to coordination compounds by emulsifying concentrated or dilute oil solutions of the sulfonates with aqueous solutions or suspensions of any suitable metal salt or base followed by dehydration in the manner already described.

When preparing coordination compounds by the methods ofthe present invention care must be taken not to select salts which wall react with the sulfonate to form water-insoluble salts of the polyvalent metal already combined with the sulfonic acids. Thus, for example, lithium sulfate should not be chosen to make a coordination compound with calcium sulfonates because by double decomposition lithium sulfonate and calcium sulfatewould be formed instead of the desired complex sulfonate.

Thev materials listed below have been found to be effective to a greater or less degree in fluidizing, that is, reducing materially the consistency of a solid 30% concentrate of normal calcium sulfonates in oil. The metal sulfonates listed in table II were prepared by acid treating an oil, neutralizing with lime, filtering, and concentrating by distillation. Portions of the solid concentrate were heated to about 200 F. to liquefy them and were then emulsified with small amounts of 10 to 20% aqueous solutions of the desired metal compounds and heated to about TAaLn II Compound Used giggi 1 Calcium hydroxide Onl all h 2 Calcium chloride Poo g t 3 Calcium chloride and calcium hydroxide Very good g Lithium hydroxide cod. 6 7 8 9 l0 ll 12 i3 14 other salts or bases are extremely fluid, while theoil concentrates of the normal sulfonates are gelatinous in nature, indicates that the added metal compounds are present as weak or secondary components or possibly as double salts,

rather than as occluded material. It would seem that the occlusion of inorganic salts would not contribute to oil-solubility. The inorganic compounds cannot be introduced into normal metal sulfonate concentrates except in the presence of appreciable amounts of water, indicating that ionization is a factor in the formation of the coordination compounds. Neither chloride nor hydroxyl ions can be detected in water which has etc.

"though prolonged contact higher temperature does produce hydrolysis.

In the absence of definite proof of structure the complexes of the present invention can be identifled only as metal sulfonates containing more than the theoretical amount of metal. It is possible that they may be represented by one or both of the following formulae. using calcium sulfonate as an example; 4

HBMPGBOP '0. ;Ca(OH);

In connection with the manufacture of the calcium sulfonate complexes by the above procedures, copious foaming occurs when boiling the water out of the soaps, making the operation extremely difficult. Such foaming can be reduced to a negligble amount by adding a small amount of a suitable defoaming agent prior to dehydration.

Other oil-soluble hydrocarbon sulfonic acids suitable for preparing the sulfonate complexes of the present invention may be produced by sulfon-- ating alkyl aromatic hydrocarbons, such as alkyl benzenes, alkyl naphthalenes, alkyl anthracene, alkyl phenanthrenes, alkyl picenes, alkyl chrysenes, alkyl biphenyls, etc.,' provided the number of carbon atoms in the alkyl chain or chains is sufficient to render the resulting sulfonic acids and their salts soluble in hydrocarbon oil. It is desirablethat at least one alkyl radical be rela- I tively long, i. e., contain at least 8 or more carbon atoms, not only because of solubility in hydrocarbon oils, but, also for the reason that'long alkyl chains improve the anti-ringsticking efficiency of the salts formed with the sulfonic acids. Thus, an aromatic hydrocarbon suitable for the production of highly eflicient sulfonic acids may be produced by condensation of aromatic hydrocarbons with chlorinated parafdn wax, alkyl chlorides such as octyl, decyl, cetyl, etc., chlorides, fatty alcohols, long chain olefines such as may be obtained in the cracking of wax,

Suitable condensing agents may be employed, such as Friedel-Craits catalysts, sulfuric acid, phosphorus pentoxide, phosphoric acid, etc.

The hydrocarbon sulfonic acids may, if desired, contain substitution radicals such as bydroxyl, primary, secondary or tertiary amine, ether, sulfide, hydrosulfide, disulfide, halogen, etc., radicals which may be attached to the ring or to side chains or both. For example, paraffin wax substituted naphthalene mono sulfonic acids which contain a sulfonic radical attached to one ring of the naphthalene nucleus and a hydroxyl or amino radical attached to the other ring may be employed.

Phenol sulfonic acids such as tetraisobutyl phenol-sulfonic acid, wax phenol sulfonic acid, and the like, as well as olefin sulfonic acids, naphthene sulfonic acids, terpene sulfonic acids, etc., are also suitable.

In preparing lubricating oils, according to the present invention, the soaps or soap oil concentrates are stirred into a prepared mineral lubricating oil and the solution is effected by agitation, a slight elevation of temperature being produced, if desired, to facilitate the operation.

Generally, the addition agents of the resent invention are most advantageously blended with lubricating 011 base stocks in concentrations between the approximate limits of 0.02% and 5.0% and preferably from 0.1% to 2.5%, although larger amounts may be used for some purposes. The exact amount of addition agent required for maximum improvement depends to a certain extent on the particular products used, the nature of the lubricating oil base stock and the general operating conditions of the engine in which the lubricant is to be employed.

As has been pointed out elsewhere in this specification, it is often convenient to prepare concentrates of the additives in oil, containing, say, 25 to of effective addition agent, the concentrate later being added to a suitable lubricating oil base stock to give a finished blend containing the desired percentage of additive. Thus, when using a 35% concentrate, 4.3% of this material may be blended with a suitable base stock to give a finished oil containing 1.5% of effective addition agent.

In the following examples are described various preparations of products in accordance with this invention and the results obtained on testing the same in various lubricating oil blends. It is to be understood that these examples, given for illustrative purposes only, are not to be construed as limiting the scope of the invention in any way.

EXAMPLE 1 A solution of sodium sulfonates was prepared by extracting with aqueous alcohol a sodium carbonate neutralized, sulfuric acid-treated phenol railinate of-a naphthenic distillate oil, the original oil having a Saybolt viscosity of 800 seconds at F. The extract was diluted with one and one-half volumes of water, calcium sulfonates precipitated with calcium chloride solution and the precipitate dehydrated at 310 F. in the presence of oil, calcium chloride brine and 1% of lime (Ca(0H)z) based on soap. After filtration a fluid concentrate was obtained containing a calcium sulfonate-calcium chloridecalcium hydroxide complex. Analysis of this concentrate is shown below:

TABLE III Calcium sulfonate per cent 29.8 Sodium sulfonate do 1.0 Calcium content do 1.71 Sodium content do 0.05 Calcium in excess of theoretical do 35 Sulfur do 2.13 Chlorine do 0.80 Neutralization value Mg. KOH/g .44. 1 2.6 Consistency, fluid.

Alkaline.

EXAMPLE 2 About 24 kg. of a crude aqueous-alcohol extract of sodium sulionates obtained by extraction of acid oil during the manufacture 01' white 011 and containing about sodium sulionates, 2% mineral oil; 6% inorganic sodium salts (NaaSOa etc.), 41% isopropyl alcohol and 41% water was mixed with 27 liters of water and heated to 155 F. A solution of 835 grams oi calcium chloride in 2 liters of water was added, causing precipitation of calcium suli'onates. The mixture was cooled to room temperature and amajor part of the supernatant water decanted. Then 10 kg. of a solvent-extracted naphthenic type mineral lubricating oil (viscosity about 45 seconds Saybolt at 210 F.) and 35 grams of calcium hydroxide were added and the mlxtureheated with stirring to effect dehydration. During this step a solution of grams of calcium chloride in 150 cc. of water was added and the dehydration then completed, heating being conducted at a maximum temperature oi 260 F. The product was filtered to give a mineral oil concentrate containing about 26 to 27% sodium sultonatecalcium sulfonate-calcium chloride-calcium hydroxide complex. This concentrate was mixed with another batch of the same type of sulfonate in Example 1 was steamed and distilled to remove alcohol and most of the water and then reagitated with more concentrated aqueous alcohol (80-85%) and stored to separate insoluble salts. The alcohol solution was mixed with oil and heated to drive oil the alcohol. The concentration of sodium sulfonates was then adjusted with sufllclent oil to give a 30 to concentrate and emulsified with 100% excess of a 20% calcium chloride solution. The emulsion was then agitated and heated to 255 F. whereupon most of the sodium chloride separated out as a salt break" which was drawn off with the excess calcium chloride solution. After sepaartion oi the salts. 0.3% lime was added to the residue and the mixture was heated to 310 F. to drive of! the water and th resulting mass was filtered.

Method B.-An emulsified solution oi sodium sulionate in oil obtained as in Method A was heated to 250 F. at which time 1.5% lime was added. Then, without removing the salts, the heating was continued to 310 F. until the mass was dehydrated.

Method C.--A complex was prepared as in Method B except that only excess of calcium chloride was used instead of 100%.

The concentrates obtained in the above cases were fluid and analyzed as follows:

Tana: V

Batch Ca Na Ca Na Total Alk. Excess Cl No Manufacture Sulio Sulio- Con- Con- Excess Neut. Calrom Connate natc tent tent Ca No. Lime; tent 1 1007s col 00571; s it]? k t255F 31"? ls' l li s z? 3 3 0" 0 0 xcess a me, a rea a B. 1009; Excess CaCi: Dehyfirated with Salt, 1.5% Lime added at 250 1 33.4 0.8 2.27 0.045 43 1.0 10 0.00 C. 50% Excess CaCl Dehydrated with Salt, 1.5% Lime Added at Excess Grav- Color Batch Vis. at V1.0. at B. S. Manufacture (5221511151 Ash Sulfur 213;,I 100]. F Water (I W.

Per cent Per cent Per cent Per cent Per cent .4.. 100% Excess 0501,, 0.35% Lime, Salt Break at 255 F 25 0.00 2.40 10.2 1,480 118.4 0% R 0.25 B 100% Excess CaCl, Dehydrated with Salt, 1.5% Lime Added at 250 1 0. 81 2.00 14.1 1,013 140.0 5% 0.11 (l 50% Excess CaCi, Dehydrated with Salt, 1.5% Lime Added at 250 1 5.00 2.44 15.0 054 87.1 3 0.37 0.04

1 Percent in excess of theoretical. 1 Calculated from neutralization number. Calculated from chlorine content".

concentrate prepared by essentially the same Exun, 4 procedure. Analysis of the composite concen- LE g t was as follows; In the following tests, lubricating oil blends TABLE Iv, containing addition agents of the present inven? Per cent tion were tested in a single cylinder Caterpillar Calcium sulfonate 20 2 Diesel engine run under the following conditions: sodium suuonate 19.8 B. H. P. output, 1000 R. P. M., 165 F. oil Calcium content temperature and 180 F. jacket temperature for Sodium content o 31 126 hour periods. After each test was completed Calcium in excess of theoretical the engine parts were examined and given desulfm. 1.85 merit ratings based on their condition. The inchlonne Q61 dividual ratings were weighted according to their Consistency, flum relative importance and an overall rating calculated from them. It should be pointed out that EXAMPLE 3 the lower the demerit rating the better the en- Three batches of a concentrate of calcium sulfonate-calclum chloride-calcium hydroxide complex were prepared by emulsifying mahogany sodium sulfonates in oil with calcium chloride and lime according to the following methods:

Method A.-An aqueous alcoholic solution (50% alcohol) 0! sodium sulionates prepared as gine condition and hence the better the oil performed in the engine. In all of these tests except two the base oil was a solvent extracted well refined parafllnic type oil of S. A. E. 30 viscosity grade. In the other two tests the base oil was of exactly the same type prepared in the same manner from the same crude source but was or S. A. E. 20 grade. Results of these tests are shown in the following table:

TABLE VI 126 hour single cylinder Caterpillar engine tests Engine Demerit Ratings Oil Blend Overall Ring Zone Base Oil 2. 24 2.32 Base ll+l.5% of calcium suifonate compier (4.4% of concentrate of Example 3B). 0. 97 0. 56 Base '1 (')+2 0 of Auxiliary Additives (H-1.5% oi ormul calcium sullonnte. 1.63 1.26 Base Oil )+2% of Auxiliary Addithes (H-1.5% of calcium sulionato complex (6% of concentrate of Example 2) 0. 61 0.23 Base 0ii+0.85% of reaction product of PISI and Barium tert. octyi phenol sulfide )+1.5% calcium sullonnte complex (4 45% of concentrate of Example 30) 0.52 0.10

1 S. A E. 20 grade in these two tests; S. A. E. 30 grade in oihyer tests.

0 phoric acid plus 1% of the reaction product of sulfur with a 40% concentrate of barium tert. octyl phenate in oil.

Prepared by reaction of 0.4 mole of P 8 with 1 mole oi. barium tert. octyl phenol sulfide in oil solution.

It will be readily observed from the above test results thatthe performance of the base oil in the engine was materially improved by incorporation of a sulfonate coordination compound of the present invention. It will also be noted that- EXAMPLE5 In essentially the same manner as described in previous examples, portions of a gel-like oil concentrate containing about 30-33% of normal calcium mahogany sulfonates were treated with aqueous solutions of various metal salts and bases and the treated products dehydrated to give fiuid concentrates of coordination compounds. The coordination compounds were then blended in an S. A. E. 10 grade of solvent extracted naphthenic base lubricating oil and submitted to bearing corrosion tests.

The bearing corrosion tests were conducted as follows: 500 cc. of oil to be tested was placed in a glass oxidation tube (13" long and 2%" diameter) fitted at the bottom with a A" bore air inlet tube perforated to facilitate air distribution. The oxidation tube was then immersed in a heated bath so that the oil temperature was maintained at 325 F. during the test. Two quarter sections of automotive bearings of copper-lead alloy of known weight having a total area of. 25 sq. cm. were attached to opposite sides of a stainless steel rod which was then immersed in the oil and rotated at 600 R. P. M., thus providing sufficient agitation of the sample during the test. Air was then blown through the oil at the rate of 2 cu. it. per hour. To increase the severity of the test, the bearings were washed and weighed after 4 hours and. then polished and reweighed before continuing for another four hour period. The results show the cumulative weightless at the end of four and eight hours.

The results of the bearing corrosion tests are given in the following table. In each case the oil blend contained 1.5% of metal sulfonate (about 5% of the oil concentrate). The percentages of treating agent are based on the weight of calzinc salt of tert. octyl phenol sulfide thiophos i0 cium sulfonate used as starting material. It will be seen from the results of these tests that the sulfonate coordination compounds were considerably less corrosive than the original normal calcium sulfonate.

Although in-most instances the addition agents of the present invention will of themselves impart sufiicient improvement to lubricating oils to give very satisfactory results, still greater improvement may often be obtained by employing these addition agents in conjunction with other agents of the detergent type such as metal soaps, metal phenates, metal alcoholates, metal phenol sulfides, metal organo phosphates, thiophosphates, phosphitesand thiophosphites, metal sulfonates, metal thioqarbamates, metal xanthates, and thioxanthates, and the like.

Thus the addition agents of our invention may be used in mineral lubricating oils in conjunction with one or more of the following representative materials:

The lubricating oil base stocks used in the compositions of this invention may be straight mineral lubricating oils or distillates derived from parafiinic, naphthenic, asphaltic or mixed base crudes, or if desired, various blended oils may be employed as well as residuals-particularly those from which asphaltic constituents have been carefully removed. The oils may be refined by conventional methods using acid, alkali and/or clay or other agents such as aluminum chloride, or they may be extracted oils produced for exampl by solvent extraction with solvents of the type of phenol, sulfur dioxide, furfural, dichloro ethyl ether, nitrobenzene, crotonaldehyde, etc. Hydrogenated oils or white oils may be employed as well as synthetic oils prepared, for example, by the ,treated diisobutylene.

polymerization of olefins or by the reaction of oxides of carbon with hydrogen or by the hydro genation of coal or its products. In certain instances cracking coil tar fractions and coal tar or shale oil distillates may also be used. Also for special applications, animal, vegetable or fish oils or their hydrogenated or voltolized products may be'employed, either alone or in admixture with mineral oils.

For the best results the base stock chosen should normally be that oil which without the new addition agents present gives the optimum performance in the service contemplated. However, since one advantage of the agents is that their use also make feasible the employment of less satisfactory mineral oils or other oils, no strict rule can be laid down for the choice of the base stock. Certain essentials must of course be observed. The

oils must possess the viscosity and volatility characteristics known to-be required for the service contemplated. The oil must be a satisfactory solvent for the addition agent, although in some cases auxiliary solvent agents may be used. The lubricating oils, however they may have been produced, may vary considerably in viscosity and other properties depending upon the particular use for which they are desired, but they usually range from about 40 to 150 seconds Saybolt viscosity at 210 F. For the lubrication of certain low and medium speed Diesel engines the general practice has often been to use a lubricating oil base stock prepared from naphthenic or aromatic crudes and having a Saybolt viscosity at 210 F. of 45 to 90 seconds and a viscosity index of 0 to 50. However, in certain types of Diesel service, particularly with high speed Diesel engines, and in aviation engine and other gasoline engine service, olls of higher viscosity index are often I preferred, for example, up to 75 to 100, or even higher viscosity index.

In addition to the materials to be added according to the present invention, other agents may also be used such as dyes, pour depressors, heat thickened fatty oils, sulfurized fatty oils, organo metallic compounds, metallic or other soaps. sludge dispersers, antioxidants, thickeners, viscosity index improvers, oiliness agents, resins, rubber, olefin polymers, voltolized fats, voltolized cohol, arylic alcohols, such as naphthenic alcohols; and aryl substituted alkyl alcohols, for instance, phenyl octyl alcohol, or octadecyl benzyl alcohol or mixtures of these various alcohols, which may be pure or substantially pure synthetic alcohols. Certain mixed naturally occurring alcohols such as those found in wool fat (which is known to contain a substantial percentage of alcohols having about 16 to 18 carbon atoms) and insperm oil-(which contains a high percentage of cetyl alcohol) may be used. Al though it is preferable to isolate the alcohols from those materials, for some purposes the wool fat, sperm oil or other natural products rich in alcohols may be used per se. Products prepared synthetically by chemical processes may also be used such as alcohols prepared by the oxidation of petroleum hydrocarbons, e. g., parafiln wax, petrolatum, etc.

These assisting agents serve to enhance the detergent and sludge dispersive qualities and aid the solubility of the metal-containing addition agents and at the same impart some oiliness properties to the lubricating oil compositions.

Although the present invention has been described with a certain degree of particularity, it is to be understood that the present disclosure has been made only by way of example and that numerous changes in the details and other feamineral oils, and/or voltolized waxes and colloidal solids such as graphite or zinc oxide, etc. Specific examples of such other compounds include dibenzyl disulfide, sulfurized sperm oil, voltolized sperm oil, phenyl alpha naphthylamine, polyisobutylene, polymerized lauryl methacrylate, diamyl trlsulflde, sulfurized wax olefins, tricresyl phosphate, 2, 6-di tert. butyl-4-methy1 phenol, and the reaction product of phenol with sulfur chloride Solvents and assisting agents, such as esters, ketones, alcohols, aldehydes, halogenated or nitrated compounds, and the like, may also be employed.

Assisting agents which are particularly desirable are the higher alcohols having eight or more carbon atoms and preferably 12 to 20 carbon atoms. The alcohols may be saturated straight and branched chain aliphatic alcohols such as octyl alcohol (CsH17OH), lauryl alcohol cetyl alcohol (CmHaaOH), stearyl alcohol, sometimes referred to as octadecyl alcohol,

(CraHazOH) tures of the invention may be resorted to without departing from the spirit and scope of the invention as hereinafter claimed The nature and objects of the present invention having thus been set forth and a specific illustration of the sam given, what is claimed as new and useful and desired to be secured by Letters Patent is:

1. A method of preparing a fluid concentrate of a complex chemical product from an alkaline earth metal salt of a petroleum sulfonic acid which comprises emulsifying an oil-soluble mineral oil solution containing 1 molecular proportion of said salt with 0.2-1 molecular proportion of an alkaline earth metal chloride in the form of a 10 to 30% aqueous solution, by weight heating the emulsion in the presence of 0.3 to 1.5%, based on the alkaline earth metal sulfonate present. of an alkaline earth metal hydroxide at a temperature of at least 260 F. and for a sufficient time to substantially completely dehydrate the same, and filtering off insoluble material.

2. A method according to claim 1 in which all of the alkaline earth metal compounds involved are calcium compounds.

3. A method of preparing a fluid concentrate of a complex chemical product which comprises emulsifying a solution of 1 molecular proportion of sodium salt of an oil-soluble petroleum sulfonic acid in mineral oil with a sufliclent amount of calcium chloride, in the form of a 10 to 30% aqueous solution by weight, to convert all of the sodium sulfonate to calcium suli'onate and to provide an excess of 20 to of calcium in the emulsion, and heating the emulsion containing calcium petroleum sulfonate and calcium chloride in the presence of 0.3 to 1.5% of calcium hydroxide, based on the amount of calcium sulfonate present, at 260310 F. until dehydration is substantially complete, and filtering.

4. As a new composition of matter, a complex chemical product formed by the method of claim 1.

5. As a new composition chemical product formed claim 2.

of matter, a complex by the method of 14 6. As a new composition of matter, a. complex chemical product formed by the method of I REFERENCES CITED 1 claim 3. The following references are of record in the 7. A mineral lubricating 011 containing from fil hi p nt: 3.32) at; 1121 15 5% of the product formed by the meth- 5 UNITED STATES PATENTS a. A mineral lubricating oil containing from Number Name D t 0.02% to 2.5% of the product formed by the meth- 1,367,695 Dowell J 3 19, 1932 0d of claim 2,270,577 Bergstrom et al. Ja,n. 20, 1942 9.'A mineral lubricating oil containing from 10 2,233,199 Flett May 19, 1942 0.02% to 2.5% of the product formed by the meth- 2,322,307 Neely a1 e 22, 19 0d of claim v 2,356,685 Neely et al Aug. 22, 1944 2,366,191 Jenkins Jan; 2, 1945 JOHN ZIMMER- FOREIGN PATENTS EJNAR W. CARLSON. 15 GORDON w. DUNCAN. Number Date 553,234 Great Britain May 13, 1943 

